Process for the preparation of amino-fluoro-s-triazine dyes by reaction of cyanuric fluoride with an amino dye and an amide in one operation

ABSTRACT

A process for the preparation of dyes of the formula ##STR1## in which D is a dye radical and R 1  and R 2  independently of one another is hydrogen or C 1-4  -alkyl, which comprises reacting cyanuric fluoride of the formula ##STR2## simultaneously with a dye of the formula ##STR3## and with an ammonium salt of an amine of the formula 
     
         H.sub.2 N--R.sub.2                                         (4) 
    
     in a neutral to alkaline medium, to give dyes of the formula (1) as single compounds in good yields in one operation. The novel process has the advantage of being able to be carried out as a &#34;one-pot process&#34; in a closed reaction vessel so that the apparatus is simple and immission by cyanuric fluoride is excluded.

This is a continuation of application Ser. No. 268,306, filed 5-29-81.

The invention relates to a process for the preparation of dyes of theformula ##STR4## in which D is a dye radical and R₁ and R₂ independentlyof one another is (sic) hydrogen or C₁₋₄ -alkyl, which comprisesreacting cyanuric fluoride of the formula ##STR5## simultaneously with adye of the formula ##STR6## and with an ammonium salt of an amine of theformula

    H.sub.2 N--R.sub.2                                         ( 4)

in a neutral to alkaline medium.

Dyes of the formula (1) are prepared by known processes (cf., forexample, German Offenlegungsschrift No. 2,557,141) by subjectingcyanuric fluoride of the formula (2) to condensation with a dye of theformula (3), and subjecting the primary condensation product tomonocondensation with an amine of the formula (4), or by carrying outthe two condensations described in reverse sequence. The condensationsare carried out in aqueous solution. Because the three fluorine atoms onthe triazine ring have different reactivities, the reaction temperaturechosen is 0° to 5° C. for the first condensation, and about 0° C. toroom temperature, depending on the nature of the radical R₂, for thesecond condensation. The procedure in practice is initially to introducethe amino dye in aqueous solution into the reaction vessel, to addcyanuric fluoride dropwise until reaction is complete and then to addthe amine for the second condensation. The reverse sequence ofcondensations is carried out in a corresponding manner.

The known process has a disadvantage. Since the amine is used in excess,the pH value of the reaction mixture rises sharply when the amine isadded. Detachment of the fluorine atoms from the triazine ring byhydrolysis is thereby favoured, and as a result some of thedifluorotriazine dye or of the cyanuric fluoride is "hydrolysed", and areduced yield results.

We have found that the abovementioned disadvantage can be avoided by thenovel process defined above. This process is a single-stage processwhich is carried out by initially introducing the amino dye and theamine in solution into the reaction vessel and adding cyanuric fluoridedropwise until reaction is complete. Since two fluorine atoms of thecyanuric fluoride are simultaneously replaced, from the start thereaction is carried out between about 0° C. and room temperature.

The novel process has the advantage that it can be carried out as a"one-pot process" in a closed reaction vessel. The apparatus istherefore simple, and immission by cyanuric fluoride is excluded.

The condensation in the process takes place instantaneously and the dyeof the formula (1) is formed as a single compound.

It would have been expected that, under the given conditions, the veryreactive cyanuric fluoride would react immediately with any reactant,i.e. amino dye or amine, when it is added dropwise to the reactionmixture, so that a mixture of primary condensation products of theformulae ##STR7## and ##STR8## is formed which, because of the adversestoichiometric proportions, further reacts only very slowly. It wouldfurthermore have been expected that the primary condensation products ofthe abovementioned formulae would partly react further with the samereaction partner of the cyanuric fluoride as initially, so thatundesired symmetric bicondensation products are formed. It would alsohave been expected that the reaction would proceed with a considerabledelay, and that the yield of the desired end product of the formula (1)would be significantly lower compared with that in the conventionalprocess.

Surprisingly, it is found that this is not the case, and that, rather,the reaction mixture reacts smoothly and rapidly and the dyestuff of theformula (1) is obtained as a single compound in good yield in oneoperation.

The reaction according to the invention can be carried out in organicsolvents, for example diethyl ether or acetone, or in aqueous solution.Preferably, the cyanuric fluoride is introduced into an aqueous solutioncontaining the amino dye and the ammonium salt of the amine. The amineis continuously set free from the ammonium salt by constant addition ofan alkali, for example sodium hydroxide solution, during thecondensation. In one embodiment, the pH value of the aqueous solution isadjusted to 7 to 10, preferably 8 to 9.

Amines of the formula (4) are: ammonia, methylamine, ethylamine,propylamine, isopropylamine, butylamine, isobutylamine, sec.-butylamineand tert.-butylamine.

Ammonium salts are the salts of inorganic acids, in particular thechlorides, sulphates, carbonates and phosphates. Examples of ammoniumsalts of amines which can be used according to the invention are:ammonium chloride, ammonium sulphate, ammonium carbonate, methylammoniumchloride, methylammonium sulphate, ethylammonium chloride andβ-hydroxyethylammonium chloride. Ammonia is preferably used as the amineof the formula (4), and is preferably employed in the form of ammoniumchloride.

The dyestuffs of the formula (3) used are, in particular, those in whichthe radical D is the radical of a dye of the monoazo or polyazo, metalcomplex azo, anthraquinone, phthalocyanine, formazan, dioxazine,phenazine or stilbene series.

Dyes of the formula (3) in which the radical D contains groups whichconfer solubility in water are preferably used as the startingmaterials.

A group which confers solubility in water is, in particular, thesulphonic acid group.

The alkyl substituent R₁ having 1 to 4 carbon atoms in formula (1) or(3) is: methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec.-butyl ortert.-butyl.

The radical of a dye D in formula (1) or (3) can contain furthersubstitutents, examples of which are: alkyl groups having 1 to 4 carbonatoms, such as methyl, ethyl, propyl, isopropyl and butyl, alkoxy groupshaving 1 to 4 carbon atoms, such as methoxy, ethoxy, propoxy, isopropoxyand butoxy, acylamino groups having 1 to 6 carbon atoms, such asacetylamino and propionylamino, benzoylamino, halogen, such as fluorine,chlorine and bromine, nitro, cyano, trifluoromethyl, sulfamoyl,carbamoyl, ureido, amino, hydroxyl, carboxyl, sulfomethyl and sulfo. Inparticular, the radical D contains sulfonic acid groups as substituents.

An aminoazo dye is preferably used as the dye of the formula (3). Inparticular, dyes of the formula (3) in which D is the radical of amonoazo or disazo dye are used as starting materials.

Dyes of the formula (3) in which R₁ is hydrogen, methyl or ethyl arealso preferred.

In other preferred embodiments, an aminoazo dye of the formula ##STR9##in which D₁ is the radical of a diazo component of the benzene ornaphthalene series, is used, in particular, an aminoazo dyes of theformula ##STR10## in which D₁ is the radical of a diazo component of thebenzene or naphthalene series, is used, and, especially, the dye of theformula ##STR11## is used.

Dyes of the formula (3) are, in particular, dyes of the followingstructural types: ##STR12## Metal complexes of dyes of the formulae##STR13## and ##STR14## Preferred metal atoms are Cu (1:1 complex) or Crand Co (1:2 complexes). Cr and Co complexes can contain one or tworadicals of the azo compound of the abovementioned formula, i.e. theycan be built up symmetrically, or unsymmetrically with any other ligandgroupings. ##STR15## The fused-on rings indicated by broken lines arenaphthalene systems which are alternatively possible. ##STR16## In thisformula, Pc represents the Cu phthalocyanine radical or the Niphthalocyanine radical. The total number of substituents on the Pcskeleton here is 4. ##STR17##

The alkyl or aryl radicals of the dyes of the abovementioned formulaecan be further substituted, in particular by the substituents mentionedin the explanation of D in formula (1) or (3).

The following azo dyes of the formula (3) are particularly important:##STR18## in which K is the radical of a coupling component of thebenzene, naphthalene or heterocyclic series, acyl is a low-molecularaliphatic acyl radical having at most 3 carbon atoms or an aromaticradical having at most 8 carbon atoms, and R₁ is as defined in theexplanation of formula (1), and the metal complex azo dyes of theformulae ##STR19## in which R₁ and acyl are as defined above and Me isCu, Cr or Co.

In the preparation of the preferred reactive dyes of the formula (1) inwhich D is the radical of an azo dye, in particular of a monoazo ordisazo dye, the diazotisation of the intermediates containing adiazotisable amino group is as a rule effected by the action of nitrousacid in aqueous-mineral acid solution at a low temperature, and thecoupling is carried out at weakly acid, neutral or weakly alkaline pHvalues.

The condensation (sic) of cyanuric fluoride of the formula (2) with thedyes of the formula (3) and the amines of the formula (4) are preferablycarried out in aqueous solution or suspension, at low temperature and ata neutral to alkaline pH value, in a manner such that one fluorine atomremains as a detachable radical in the finished dye of the formula (1).Hydrogen fluoride set free during the condensation is advantageouslycontinuously neutralised by addition of aqueous alkali metal hydroxides,carbonates or bicarbonates.

If the reactive dyes of the formula (1) in which D is the radical of anazo dye contain complex-forming groups, for example hydroxyl or carboxylgroups, in the ortho-ortho'-position relative to the azo group, it isalso possible to prepare metal complexes of the azo dyes of the formula(1), by treating the azo compounds which are obtained according to theinvention and which contain complex-forming groups in theortho-ortho'-position relative to the azo group with metal-donatingagents before or, where relevant, after the condensation with cyanuricfluoride of the formula (2).

Copper complexes of azo dyes of the formula (1) are of particularinterest. As well as the above-mentioned metallisation method,dealkylating metallisation and, for the preparation of copper complexes,oxidative coppering can also be used.

The dyes of the formula (1) are fibre-reactive, since they contain adetachable fluorine atom in the s-triazine radical.

Fibre-reactive compounds are to be understood as meaning those compoundswhich are capable of reacting with the hydroxyl groups of cellulose orwith the amino groups of natural or synthetic polyamides to formcovalent chemical bonds.

The reactive dyes of the formula (1) are distinguished by a highreactivity, and they produce dyeings with good wetfastness andlightfastness. They also have a good fixing ability and product dyeingswith a remarkably good depth of shade.

The reactive dyes of the formula (1) are suitable for dyeing andprinting a wide variety of materials, such as silk, leather, wool, highmolecular weight polyamide fibres and high molecular weightpolyamide-urethanes, and especially cellulose-containing materials witha fibrous structure, such as linen, wood pulp, regenerated celluloseand, in particular, cotton. They are suitable both for the exhaustprocess and for dyeing by the pad-dyeing process, in which the goods areimpregnated with aqueous dye solutions, which may also contain salts,and the dyes are fixed after treatment with an alkali or in the presenceof alkali, if necessary under the action of heat.

They are also suitable for printing, in particular on cotton, but alsofor printing on nitrogen-containing fibres, for example wool, silk ormixed fabrics containing wool.

It is advisable to rinse the dyeings and prints thoroughly with cold andhot water, if necessary with the addition of a dispersing agent whichpromote diffusion of the non-fixed portions.

In the examples which follow, the preparation of the monoazo or disazointermediates is not described in every case, but the method followsreadily from what has been stated above.

In the following examples, the parts are by weight and the temperaturesare in degrees Centigrade.

EXAMPLE 1

75.2 parts of the dye of the formula ##STR20## are dissolved in 700parts of water at 20° C. under neutral conditions. After 5.6 parts ofammonium chloride have been added, the reaction solution is cooled to 0°to 5° C. and the pH value is adjusted to 8.5 with 2.5 parts by volume of2N sodium hydroxide solution.

14.2 parts of cyanuric fluoride are added dropwise in the course of 35minutes, with very good stirring. The temperature is allowed to rise to20° C., and the pH value is kept at 8.5 by addition of 147 parts byvolume of 2N sodium hydroxide solution. When the reaction has ended, thedye solution is adjusted to a pH value of 7.5 with 2.8 parts by volumeof 1N hydrochloric acid. The reactive dye of the formula ##STR21## isnow salted out by sprinkling in potassium chloride, and is filtered off,washed, and dried in vacuo. It is a red powder which dyes cotton andregenerated cellulose in bluish-tinged red shades.

Dyes with similar properties are obtained if the amino dyes listed incolumn 2 in Table 1 which follows are subjected to condensation withequivalent parts of cyanuric fluoride in the presence of ammonium saltsin accordance with the statements of Example 1. Equivalent amounts ofammonium bromide, ammonium carbonate, ammonium fluoride, ammoniumbicarbonate, ammonium bisulfate, ammonium nitrate, primary ammoniumphosphate, secondary ammonium phosphate or ammonium sulfate, forexample, can be used as the ammonium salts.

Example 1 is repeated using, instead of 5.6 parts of ammonium chloride,equivalent amounts of one of the ammonium salts in the following list:methylamine hydrochloride, dimethylamine hydrochloride, ethylaminehydrochloride, diethylamine hydrochloride, propylamine hydrochloride,isopropylamine hydrochloride, butylamine hydrochloride, isobutylaminehydrochloride and sec.-butylamine hydrochloride. The same results areachieved and the dyes substituted correspondingly to the amine used areobtained.

                  TABLE                                                           ______________________________________                                                                        Colour                                                                        shade on                                      No.  Amino dye                  cellulose                                     ______________________________________                                         2   1-Amino-3-acetylaminobenzene-6-sulfonic                                                                  yellow                                             acid → 1-ethyl-3-sulfomethyl-4-methyl-                                 6-hydroxy-pyrid-2-one-5-carboxylic acid                                       amide (hydrolysed)                                                        3   2-Amino-1-sulfo-5-aminomethyl-naphthalene →                                                       yellow                                             1-ethyl-3-aminocarbonyl-4-methyl-6-hydroxy-                                   pyrid-2-one (hydrolysed)                                                  4   2-Amino-5-aminomethyl-1,7-disulfo-naph-                                                                  yellow                                             thalene → 1-ethyl-3-aminocarbonyl-4-                                   methyl-6-hydroxypyrid-2-one (hydrolysed)                                  5   1-Amino-3-acetylaminobenzene-6-sulfonic                                                                  yellow                                             acid → 1-(4'-sulfophenyl)-3-methyl-                                    pyrazol-5-one (hydrolysed)                                                6   1-Amino-3-acetylaminobenzene-6-sulfonic                                                                  yellow                                             acid → 1-(4'-sulfophenyl)-3-carboxy-                                   pyrazol-5-one (hydrolysed)                                                7   1-Amino-3-acetylaminobenzene-6-sulfonic                                                                  yellow                                             acid → 1-(2',5'-dichloro-4'-sulfophenyl)-                              3-methylpyrazol-5-one (hydrolysed)                                        8   1-Amino-3-acetylaminobenzene-6-sulfonic                                                                  yellow                                             acid → 1-(2',5'-disulfophenyl)-3-methyl-                               pyrazol-5-one (hydrolysed)                                                9   1-Aminobenzene-2,5-disulfonic acid →                                                              yellow                                             1-(3'-aminophenyl)-3-methylpyrazol-5-                                         one (sic)                                                                10   1-Amino-3-acetylaminobenzene-6-sulfonic                                                                  yellow                                             acid → 1-(4',8'-disulfonaphth-2'-yl)-3-                                methylpyrazol-5-one (hydrolysed)                                         11   1-Amino-3-acetylaminobenzene-6-sulfonic                                                                  yellow                                             acid → 1-(2'-methyl-4'-sulfophenyl)-3-                                 carboxy-pyrazol-5-one (hydrolysed)                                       12   1-Amino-3-acetylaminobenzene-6-sulfonic                                                                  yellow                                             acid → 1-(3'-sulfophenyl)-3-methyl-pyra-                               zol-5-one (hydrolysed)                                                   13   1-Amino-4-acetylaminobenzene-2-sulfonic                                                                  yellow                                             acid → 1-carboxymethyl-pyrazol-5-one-3-                                carboxylic acid (hydrolysed)                                             14   1-Amino-4-nitrobenzene-2-sulfonic acid →                                                          yellow                                             4-amino-3,5-disulfoacetoacetanilide                                           (reduced)                                                                15   1-Amino-4-acetylaminobenzene → 1-(2',5'-                                                          reddish-                                           disulfophenyl)-3-methyl-pyrazol-5-one                                                                    tinged                                             (hydrolysed)               yellow                                        16   1-Aminobenzene-2,4-disulfonic acid →                                                              reddish-                                           3-aminophenylurea          tinged                                                                        yellow                                        17   2-Aminonaphthalene-4,8-disulfonic acid →                                                          reddish-                                           1-amino-3-acetylaminobenzene                                                                             tinged                                                                        yellow                                        18   2-Aminonaphthalene-6,8-disulfonic acid →                                                          reddish-                                           1-amino-3-acetylaminobenzene                                                                             tinged                                                                        yellow                                        19   2-aminonaphthalene-3,6,8-trisulfonic                                                                     reddish-                                           acid → 3-aminophenylurea                                                                          tinged                                                                        yellow                                        20   2-Aminonaphthalene-4,6,8-trisulfonic acid →                                                       reddish-                                           1-amino-3-methylbenzene    tinged                                                                        yellow                                        21   2-Aminonaphthalene-3,6,8-trisulfonic acid →                                                       reddish-                                           1-amino-3-acetylaminobenzene                                                                             tinged                                                                        yellow                                        22   1-Aminobenzene-2,4-disulfonic acid →                                                              brown                                              1-aminonaphthalene-6-sulfonic acid →                                   1-amino-3-methylbenzene                                                  23   2-Aminonaphthalene-4,8-trisulfonic acid →                                                         brown                                              1-aminonaphthalene-6-sulfonic acid →                                   1-amino-3-methylbenzene                                                  24   1-Aminonaphthalene-2,5,7-trisulfonic                                                                     brown                                              acid → 1-aminonaphthalene-6-sulfonic                                   acid → 1-aminonaphthalene-6-sulfonic                                   acid                                                                     25   1-Amino-4-acetylaminobenzene-2-sulfonic                                                                  brown                                              acid → 1-hydroxy-7-(3'-sulfophenylamino)-                              naphthalene-3-sulfonic acid (hydrolysed)                                 26   1-Amino-3-acetylaminobenzene-6-sulfonic                                                                  orange                                             acid → 2-hydroxynaphthalene-6,8-disul-                                 fonic acid (hydrolysed)                                                  27   1-Amino-3-acetylaminobenzene-6-sulfonic                                                                  orange                                             acid → 2-aminonaphthalene-5,7-disulfonic                               acid (hydrolysed)                                                        28   1-Aminobenzene-2-sulfonic acid → 2-N                                                              orange                                             methyl-Nacetylamino-5-hydroxynaphthalene-                                     7-sulfonic acid (hydrolysed)                                             29   1-Aminobenzene-2,5-disulfonic acid →                                                              orange                                             2-acetylamino-5-hydroxynaphthalene-7-                                         sulfonic acid (hydrolysed)                                               30   2-Aminonaphthalene-1,7-disulfonic acid →                                                          orange                                             2-acetylamino-5-hydroxynaphthalene-7-                                         sulfonic acid (hydrolysed)                                               31   2-Aminonaphthalene-1,5,7-trisulfonic acid →                                                       orange                                             2-acetylamino-5-hydroxynaphthalene-7-                                         sulfonic acid (hydrolysed)                                               32   2-Aminonaphthalene-3,6,8-trisulfonic acid →                                                       orange                                             2-acetylamino-5-hydroxynaphthalene-7-                                         sulfonic acid (hydrolysed)                                               33   2-Aminonaphthalene-1,7-disulfonic acid →                                                          scarlet                                            2-acetylamino-8-hydroxynaphthalene-6-                                         sulfonic acid (hydrolysed)                                               34   2-Aminonaphthalene-1,5-disulfonic acid →                                                          scarlet                                            2-acetylamino-8-hydroxynaphthalene-6-                                         sulfonic acid (hydrolysed)                                               35   2-Aminonaphthalene-1,5-disulfonic acid →                                                          orange                                             1-acetylamino-5-hydroxynaphthalene-7-                                         sulfonic acid (hydrolysed)                                               36   1-Amino-4-methoxybenzene-2,5-disulfonic                                                                  scarlet                                            acid → 2-acetylamino-5-hydroxynaph-                                    thalene-7-sulfonic acid (hydrolysed)                                     37   1-Amino-4-methylbenzene-2,5-disulfonic                                                                   orange                                             acid → 2-acetylamino-5-hydroxynaph-                                    thalene-7-sulfonic acid (hydrolysed)                                     38   2-Aminonaphthalene-4,6,8-trisulfonic acid →                                                       orange                                             1-aminobenzene → 1-aminobenzene                                   39   1-Aminobenzene-2-sulfonic acid →                                                                  red                                                1-acetylamino-8-hydroxynaphthalene-3,6-                                       disulfonic acid (hydrolysed)                                             40   2-Aminonaphthalene-1,5-disulfonic acid →                                                          red                                                1-acetylamino-8-hydroxynaphthalene-3,6-                                       disulfonic acid (hydrolysed)                                             41   1-Aminobenzene-2,4-disulfonic acid →                                                              red                                                1-(4'-nitrobenzoylamino)-8-hydroxynaph-                                       thalene-3,6-disulfonic acid (reduced)                                    42   1-Aminobenzene-2,5-disulfonic acid →                                                              red                                                1-(3'-nitrobenzoylamino)-8-hydroxynaph-                                       thalene-3,6-disulfonic acid (reduced)                                    43   1-Aminobenzene-2,4-disulfonic acid →                                                              red                                                1-(4'-nitrobenzoylamino)-8-hydroxynaph-                                       thalene-4,6-disulfonic acid (reduced)                                    44   2-Aminonaphthalene-1,5,7-trisulfonic acid →                                                       red                                                1-(4'-nitrobenzoylamino)-8-hydroxynaph-                                       thalene-3,6-disulfonic acid (reduced)                                    45   2-Aminonaphthalene-1,5-disulfonic acid →                                                          red                                                1-(4'-nitrobenzoylamino)-8-hydroxynaph-                                       thalene-4,6-disulfonic acid (reduced)                                    46   2-Aminonaphthalene-1,5,7-trisulfonic acid →                                                       red                                                1-(3'-nitrobenzoylamino)-8-hydroxynaph-                                       thalene-4,6-disulfonic acid (reduced)                                    47   2-Amino-1-sulfo-5-aminomethyl-naphthalene →                                                       red                                                1-acetylamino-8-hydroxynaphthalene-3,6-                                       disulfonic acid                                                          48   2-Amino-1-sulfo-5-aminomethyl-naphthalene →                                                       red                                                1-benzoylamino-8-hydroxynaphthalene-3,6-                                      disulfonic acid                                                          49   2-Amino-1-sulfo-5-aminomethyl-naphthalene →                                                       red                                                1-acetylamino-8-hydroxynaphthalene-4,6-                                       disulfonic acid                                                          50   2-Amino-1,7-disulfo-5-aminomethyl-naph-                                                                  red                                                thalene → 1-benzoylamino-8-hydroxynaph-                                thalene-3,6-disulfonic acid                                              51   2-Amino-1,7-disulfo-5-aminomethyl-naph-                                                                  red                                                thalene → 1-benzoylamino-8-hydroxynaph-                                thalene-4,6-disulfonic acid                                              52   1-Aminobenzene-2,4-disulfonic acid (acid                                                                 blue                                               coupling) → 1-amino-8-hydroxynaphtha-                                  lene-3,6-disulfonic acid ← (alkaline                                     coupling) 1-amino-3-acetylaminobenzene-6-                                     sulfonic acid (hydrolysed)                                               53   N(2-Carboxy-5-sulfophenyl)-N'(2'-hydroxy-                                                                blue                                               3'-amino-5'-sulfophenyl)-ms-phenyl-                                           formazan, Cu complex                                                     54   N(2-Carboxy-5-sulfophenyl)-N'(2'-hydroxy-                                                                blue                                               3'-amino-5'-sulfophenyl)-ms-(4"-sulfo-                                        phenyl)-formazan, Cu complex                                             55   N(2-Carboxy-5-sulfophenyl)-N'(2'-hydroxy-                                                                blue                                               3',5'-disulfophenyl)-ms-(3"-aminophenyl)-                                     formazan, Cu complex                                                     56   N(2-Carboxy-4-sulfophenyl)-N'(2'-hydroxy-                                                                blue                                               5'-amino-3'-sulfophenyl)-ms-(4"-sulfo-                                        phenyl)-formazan, Cu complex                                             57   N(2-Carboxy-4-aminophenyl)-N'(2'-hy-                                                                     blue                                               droxy-3',5'-disulfophenyl)-ms-(3"-sulfophenyl)-                               formazan, Cu complex                                                     58   N(2-Carboxy-4-aminophenyl)-N'(2'-hy-                                                                     blue                                               droxy-3',5'-disulfophenyl)-ms-(2"-sulfophenyl)-                               formazan, Cu complex                                                     59   N(2-Hydroxy-3-amino-5-sulfophenyl)-N'                                                                    blue                                               (2'-hydroxy-4'-sulfophenyl)-ms-(2"-sulfo-                                     phenyl)-formazan, Cu complex                                             60   N(2-Hydroxy-3-amino-5-sulfophenyl)-N'                                                                    blue                                               (2'-hydroxy-3',5'-disulfophenyl)-ms-                                          phenylformazan, Cu complex                                               61   N(2-Hydroxy-5-sulfophenyl)-N'(2'-hy-                                                                     blue                                               droxy-3',5'-disulfophenyl)-ms-(4"-aminophenyl)-                               formazan, Cu complex                                                     62   N(2-Hydroxy-3-amino-5-sulfophenyl)-N'                                                                    blue                                               (2'-hydroxy-3',5'-disulfophenyl)-ms-(4"-                                      sulfophenyl)-formazan, Cu complex                                        63   N(2-Hydroxy-5-amino-3-sulfophenyl)-N'                                                                    blue                                               (2',5'-disulfophenyl)-ms-phenyl-formazan,                                     Cu complex                                                               64   N(2-Hydroxy-4,6-disulfophenyl)-N'(2',4'-                                                                 blue                                               disulfophenyl)-ms-(3"-aminophenyl)-                                           formazan, Cu complex                                                     65   1-Diazo-2-hydroxy-6-nitronaphthalene-4-                                                                  blue                                               sulfonic acid → 1-amino-8-hydroxynaph-                                 thalene-2,4-disulfonic acid (reduced),                                        Cu complex                                                               66   1-Diazo-2-hydroxy-6-nitronaphthalene-4-                                                                  violet                                             sulfonic acid → 1-hydroxynaphthalene-                                  4,8-disulfonic acid (reduced), Cu complex                                67   2-Aminonaphthalene-4,6,8-trisulfonic acid →                                                       reddish-                                           2-hydroxy-6-acetylaminonaphthalene-4-                                                                    tinged                                             sulfonic acid, coppered with oxidation                                                                   blue                                               (hydrolysed)                                                             68   1-Diazo-2-hydroxy-6-nitronaphthalene-4-                                                                  bluish-                                            sulfonic acid → 1-benzoylamino-8-hydroxy-                                                         tinged                                             naphthalene-3,6-disulfonic acid (reduced),                                                               violet                                             Cu complex                                                               69   2-Amino-4,6,8-trisulfonic acid →                                                                  violet                                             2-acetylamino-5-hydroxynaphthalene-7-                                         sulfonic acid, coppered with oxidation                                        (hydrolysed)                                                             70   2-Aminonaphthalene-4,8-disulfonic acid →                                                          bluish-                                            2-acetylamino-5-hydroxynaphthalene-4,8-                                                                  tinged                                             disulfonic acid, coppered with oxidation                                                                 violet                                             (hydrolysed)                                                             71   2-Aminonaphthalene-6,8-disulfonic acid →                                                          claret                                             2-acetylamino-5-hydroxynaphthalene-7-                                         sulfonic acid, coppered with oxidation                                        (hydrolysed)                                                             72   2-Aminonaphthalene-4,8-disulfonic acid →                                                          blue                                               1-amino-8-hydroxynaphthalene-3,6-di-                                          sulfonic acid, coppered with oxidation                                   73   1-Amino-4-acetylaminobenzene-2-sulfonic                                                                  navy                                               acid → 1-amino-2-methoxy-5-methyl-                                                                blue                                               benzene → 1-hydroxynaphthalene-3,6,8-                                  trisulfonic acid, coppered with demethyl-                                     ation (hydrolysed)                                                       74   1-Hydroxy-2-aminobenzene-4,6-disulfonic                                                                  ruby                                               acid → 2-amino-5-hydroxynaphthalene-7-                                 sulfonic acid, Cu complex                                                75   1-Hydroxy-2-aminobenzene-4,6-disulfonic                                                                  ruby                                               acid → 2-amino-8-hydroxynaphthalene-6-                                 sulfonic acid, Cu complex                                                76   1-Hydroxy-2-aminobenzene-4,6-disulfonic                                                                  violet                                             acid → 2-(4'-aminophenylamino)-5-hydroxy-                              naphthalene-7-sulfonic acid, Cu complex                                  77   1-Hydroxy-2-aminobenzene-5-sulfonic acid →                                                        violet                                             1-amino-8-hydroxynaphthalene-3,6-disulfonic                                   acid, Cu complex                                                         78   1-Hydroxy-2-amino-4-chlorobenzene-5-sul-                                                                 violet                                             fonic acid → 2-methylamino-8-hydroxy-                                  naphthalene-6-sulfonic acid, Cu complex                                  79   1-Hydroxy-2-amino-4-acetylaminobenzene-6-                                                                blue                                               sulfonic acid → 1-amino-8-hydroxy-                                     naphthalene-2,4-disulfonic acid, Cu complex                                   (hydrolysed)                                                             80   1-Amino-4-(3'-amino-4'-sulfophenylamino)-                                                                blue                                               anthraquinone-2-sulfonic acid                                            81   1-Amino-4-(4'-amino-3'-sulfophenylamino)-                                                                blue                                               anthraquinone-2-sulfonic acid                                            82   1-Amino-4-(3'-amino-4'-sulfophenylamino)-                                                                blue                                               anthraquinone-2,7-disulfonic acid (sic)                                  83   1-Amino-4-(4'-amino-3'-sulfophenylamino)-                                                                blue                                               anthraquinone-2,7-disulfonic acid                                        84   1-Amino-4-(4'-amino-2'-sulfophenylamino)-                                                                blue                                               anthraquinone-2,6-disulfonic acid                                        85   1-Amino-4-(4'-amino-3'-sulfophenylamino)-                                                                blue                                               anthraquinone-2,6-disulfonic acid                                        86   1-Amino-4-(3'-amino-2'-methyl-5'-sulfo-                                                                  blue                                               phenylamino)-anthraquinone-2-sulfonic acid                               87   1-Amino-4-(4'-amino-cyclohexylamino)-                                                                    blue                                               anthraquinone-2,6-disulfonic acid                                        88   1-Amino-4-(3'-amino-2'-methyl-5'-sulfo-                                                                  blue                                               phenylamino)-anthraquinone-2,6-disulfonic                                     acid                                                                     89   1-Amino-4-(4'-methylamino-2'-sulfophenyl-                                                                blue                                               amino)-anthraquinone-2,7-disulfonic acid                                 90   1-Amino-4-(3'-aminomethyl-2',6'-dimethyl-5-                                                              blue                                               sulfophenylamino)-anthraquinone-2,6-di-                                       sulfonic acid                                                            91   1-Amino-4-(3'-amino-2'-methyl-5'-sulfo-                                                                  blue                                               phenylamino)-anthraquinone-2,5-disulfonic                                     acid                                                                     92   1-Amino-4-(2'-aminomethyl-4'-methyl-6'-                                                                  blue                                               sulfophenylamino)-anthraquinone-2-sulfonic                                    acid                                                                     93                                                                                  ##STR22##                 turquoise blue                                94                                                                                  ##STR23##                 turquoise blue                                95                                                                                  ##STR24##                 turquoise blue                                96                                                                                  ##STR25##                 turquoise blue                                97                                                                                  ##STR26##                 greenish- tinged blue                         98                                                                                  ##STR27##                 greenish- tinged blue                         99                                                                                  ##STR28##                 turquoise blue                                100                                                                                 ##STR29##                 turquoise blue                                101                                                                                 ##STR30##                 turquoise blue                                102                                                                                 ##STR31##                 turquoise blue                                103                                                                                 ##STR32##                 turquoise blue                                104                                                                                 ##STR33##                 turquoise blue                                105                                                                                 ##STR34##                 turquoise blue                                106                                                                                 ##STR35##                 turquoise blue                                ______________________________________                                    

DYEING INSTRUCTIONS I

2 parts of the dye obtained according to Example 1 are dissolved in 100parts of water, with the addition of 0.5 part of sodiumm-nitrobenzenesulfonate. A cotton fabric is impregnated with theresulting solution so that its weight is increased by 75%, and thefabric is then dried.

Thereafter, the fabric is impregnated with a solution, at 20°, whichcontains, per liter, 5 grams of sodium hydroxide and 300 grams of sodiumchloride, and is squeezed off to a weight increase of 75%, and thedyeing is steamed at 100° to 101° for 30 seconds, rinsed, soaped in a0.3% boiling solution of an ion-free detergent for quarter of an hour,rinsed and dried.

DYEING INSTRUCTIONS II

2 parts of the dye which can be obtained according to Example 1 aredissolved in 100 parts of water.

The solution is poured into 1,900 parts of cold water, 60 parts ofsodium chloride are added, and 100 parts of a cotton fabric areintroduced into this dyebath.

The temperature is increased to 40°, 40 parts of calcined sodiumcarbonate and a further 60 parts of sodium chloride being added after 30minutes. The temperature is kept at 40° for 30 minutes, and the dyeingis rinsed, and then soaped in a 0.3% boiling solution of an ion-freedetergent for 15 minutes, rinsed and dried.

What is claimed is:
 1. A process for the preparation of a dye of theformula ##STR36## in which D is a dye radical and R₁ and R₂independently of one another is (sic) hydrogen or C₁₋₄ -alkyl, whichcomprises reacting cyanuric fluoride of the formula ##STR37##simultaneously with a dye of the formula ##STR38## and with an ammoniumsalt of an amine of the formula

    H.sub.2 N--R.sub.2                                         ( 4)

in a neutral to alkaline medium, said process being one in which thecyanuric fluoride is introduced into an aqueous solution containing theamino dye and the ammonium salt of the amine.
 2. A process according toclaim 1, wherein the pH value of the aqueous solution is adjusted to 7to
 10. 3. A process according to claim 2, wherein the pH value of theaqueous solution is adjusted to 8 to
 9. 4. A process according to anyone of claims 1 to 3, wherein ammonia is used as the amine of theformula (4), and is employed as ammonium chloride.
 5. A processaccording to any one of claims 1 to 4, wherein an aminoazo dye is usedas the dye of the formula (3).
 6. A process according to claim 5,wherein an aminoazo dye of the formula ##STR39## in which D₁ is theradical of a diazo component of the benzene or naphthalene series, isused.
 7. A process according to claim 6, wherein an aminoazo dye of theformula ##STR40## in which D₁ is as defined in claim 6, is used.
 8. Aprocess according to claim 7, wherein the dyestuff of the formula##STR41## is used.